Preheat the oven to 350 degrees F. Line one 12-cup standard muffin tin with paper cupcake liners.
Put the butter, cocoa powder and chocolate in a large bowl. Pour the boiling water over and let stand 5 minutes. Whisk until smooth, and then whisk in the sugar, vanilla and eggs. Whisk in the flour, baking powder, salt and baking soda until just combined. Stir in the chocolate chips. Divide the batter among the prepared liners so they are about three-quarters full.
Bake until a toothpick inserted into the center comes out with moist crumbs, 22 to 24 minutes. Cool in the tins 5 minutes, then remove and cool completely on a wire rack.
For the frosting: Beat the peanut butter, cream cheese and butter in a large bowl, using an electric mixer, on medium speed until smooth. Reduce the speed to low and beat in the confectioners? sugar until smooth and incorporated. Pipe or spread the frosting on the tops of the cupcakes. Sprinkle with peanuts for garnish if using.
When measuring flour, we spoon it into a dry measuring cup and level off the excess. (Scooping directly from the bag compacts the flour, resulting in dry baked goods.)
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